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Phyllobilins – the Abundant Bilin-Type Tetrapyrrolic Catabolites Of Chemical Society Reviews Phyllobilins – the Abundant Bilin -Type Tetrapyrrolic Catabolites of the Green Plant Pigment Chlorophyll Journal: Chemical Society Reviews Manuscript ID: CS-TRV-02-2014-000079.R1 Article Type: Tutorial Review Date Submitted by the Author: 02-May-2014 Complete List of Authors: Krautler, Bernhard; University of Innsbruck, Institute of Organic Chemistry Page 1 of 30 Chemical Society Reviews Phyllobilins-TutRev-BKräutler 2-May-14 1 Phyllobilins – the Abundant Bilin-type Tetrapyrrolic Catabolites of the Green Plant Pigment Chlorophyll Bernhard Kräutler Institute of Organic Chemistry and Centre of Molecular Biosciences, University of Innsbruck, Innrain 80/82, A-6020 Innsbruck, Austria E-mail: [email protected] Abstract . The seasonal disappearance of the green plant pigment chlorophyll in the leaves of deciduous trees has long been a fascinating biological puzzle. In the course of the last two and a half decades, important aspects of the previously enigmatic breakdown of chlorophyll in higher plants were elucidated. Crucial advances in this field were achieved by the discovery and structure elucidation of tetrapyrrolic chlorophyll catabolites, as well as by complementary biochemical and plant biological studies. Phyllobilins, tetrapyrrolic, bilin-type chlorophyll degradation products, are abundant chlorophyll catabolites, which occur in fall leaves and in ripe fruit. This tutorial review outlines ‘how’ chlorophyll is degraded in higher plants, and gives suggestions as to ‘why’ the plants dispose of their valuable green pigments during senescence and ripening. Insights into chlorophyll breakdown help satisfy basic human curiosity and enlighten school teaching. They contribute to fundamental questions in plant biology and may have practical consequences in agriculture and horticulture. Chemical Society Reviews Page 2 of 30 Phyllobilins-TutRev-BKräutler 2-May-14 2 Key learning points 1) Phyllobilins are linear tetrapyrroles from chlorophyll breakdown (chlorophyll catabolites), which accumulate in de-greened leaves and vegetables, as well as in ripening fruit. 2) Chlorophyll breakdown involves an amount of about 1000 million tons each year, globally. About 25 years ago, it was still a striking biological enigma. 3) In higher plants, chlorophyll breakdown follows a largely common, regulated path, named the ‘phyllobilin/PaO’ pathway. 4) Phyllobilins are related to the tetrapyrrolic heme-catabolites (called bilins), which play important biological roles. 5) Phyllobilins are suspected to have relevant physiological functions in plants; they occur in our nutrition, and may also play a role in human metabolism. Dedication Dedicated to Prof. Heinz Falk on the occasion of his 75 th birthday Page 3 of 30 Chemical Society Reviews Phyllobilins-TutRev-BKräutler 2-May-14 3 I.Introduction Have you never wondered what happens to chlorophyll, when the leaves of deciduous plants de- green and display their fall colours, or when fruit ripen and turn to an appealing yellow, red or blue (Figure 1)? The quest of finding remains of the green plant pigment has, indeed, engaged natural scientists’ interest for a considerable time. Generally, their search was guided by the idea that the breakdown products were assumed to be coloured. 1 Their failure in actually identifying chlorophyll degradation products was puzzling, as chlorophyll could not seriously be considered to disappear ‘without leaving a trace’. In fact, the global formation of chlorophyll breakdown products has been estimated to amount to about 1000 million tons, each year,2 and the seasonal disappearance of chlorophyll can be observed (and can be studied) from outer space. 3 Figure 1. Characteristic colour changes observed in fall leaves and ripening fruit are a visual sign of chlorophyll breakdown (reproduced from Chemical Biology 2008, 3, B79). Chemical Society Reviews Page 4 of 30 Phyllobilins-TutRev-BKräutler 2-May-14 4 About twenty-five years ago, in de-greening leaves, a colourless tetrapyrrole was identified as the first non-green catabolite of chlorophyll (Chl). 4 This colourless compound, now named Hv - NCC-1, was called a ‘rusty pigment’, originally, as it easily oxidized with formation of coloured product mixtures. 4, 5 When its structure could be established as a genuine Chl-breakdown product, it was classified as a ‘nonfluorescent’ Chl-catabolite (NCC), as it displayed no fluorescence (or other apparent photo-activity, see Figure 2). 4 Later studies have confirmed the broad relevance of the tetrapyrrolic NCCs as products of Chl-breakdown in higher plants. 3, 6 The original source of NCCs in specific plants was incorporated into their provisional names, e.g. Hv - NCC-1 for the most polar NCC from barley ( Hordeum vulgare , see Figure 2). Nowadays, over a dozen NCCs with different chemical structures are known, which are linear tetrapyrroles derived from Chl (for a list, see ESI, Table S1). 6 As will be delineated further below, NCCs are now classified as 1-formyl-19-oxo-phyllobilanes, as they are remarkably similar to bilanes, 6 a well known class of natural linear tetrapyrroles. 7 Figure 2: ‘Rusty pigment’ from senescent leaves of barley ( Hordeum vulgare ), later named Hv -NCC-1, was identified as the first non-green Chl-catabolite.4, 6 Page 5 of 30 Chemical Society Reviews Phyllobilins-TutRev-BKräutler 2-May-14 5 Breakdown of Chl is the visible sign of senescence and cell death in leaves and vegetables, as well as of ripening of fruit. 8 As we now know, this process degrades Chl to a variety of linear tetrapyrroles, classified as phyllobilins. 6 These Chl-catabolites, in turn, are ‘biomarkers’ for senescence in higher plants. In this review, most representative formulas of the phyllobilins are drawn in a pseudo-cyclic fashion (see Figures 2 and 3), which helps to make visual structure- correlations with the macro-cyclic precursors (Chls, pheophorbide a). However, the saturated linkages between the 5-membered heterocyclic rings show high conformational flexibility: there are three saturated linkages in phyllobilanes (see Figure 3), two in phyllobilenes, etc. In the cases of unsaturated linkages the E/Z-geometry is defined in the formulas of the corresponding Chl- catabolites, as shown below (see e.g. Figure 8 and ESI, Figure S2). Figure 3. Constitutional formula of Hv -NCC-1 in ‘pseudo-cyclic’ (left) and ‘extended’ versions (right). Considering the massive amount of Chl broken down each year on Earth, phyllobilins are also an interesting class of natural products from ecological and phytochemical points of view. 9 Systematic isolation from a variety of plant sources, and subsequent structural work, have revealed the basic chemical nature of phyllobilins.6 They are structurally related to the much better known and biologically important bilins, 7 which originate from heme-breakdown. 10 In Chemical Society Reviews Page 6 of 30 Phyllobilins-TutRev-BKräutler 2-May-14 6 spite of their importance in higher plants, the linear tetrapyrroles derived from Chl-breakdown are remarkable newcomers to the area of the heterocyclic natural products. 9 2. Phyllobilins - a long overlooked class of bilin-type tetrapyrrolic heterocycles 2.1. Phyllobilins and key enzymes in the common ‘early’ phase of chlorophyll breakdown Structure elucidation of phyllobilins has provided a solid basis for detailed studies of the biochemical processes that constitute the Chl-breakdown pathway, which undergoes its ‘early’ phase in senescent chloroplasts.11 In these plastids, the Chls are de-greened rapidly in a strictly regulated process to colourless, blue fluorescent Chl-catabolites (FCCs), which do not accumulate in senescent leaves but exist only fleetingly (see below). Along this path, the green plant pigments, Chls a and b, are first degraded to pheophorbide a (Pheo a). The macrocycle of the green Pheo a is cut open at the ‘northern’ meso-position by pheophorbide a oxygenase (PaO), an oxygen-dependent mono-oxygenase, which is highly active in senescent leaves. 12 PaO furnishes (an enzyme bound form of) the red Chl-catabolite (RCC), a linear tetrapyrrole. This 1- formyl-19-oxophyllobilin is the progenitor of all phyllobilins formed ‘later’ during Chl- breakdown. Thus, PaO is considered the key enzyme of the largely common path of Chl- breakdown in higher plants,12 named the ‘phyllobilin/PaO’ pathway. 6 However, since RCC, the product of the PaO reaction, remained bound to PaO, its detection in senescent plants was futile, at first. In fact, RCC was first prepared by chemical synthesis from Pheo a, and then it was also identified as breakdown intermediate in senescent leaves. 11 In a type of metabolic channeling PaO-bound RCC is reduced directly at its C15-meso-position by RCC-reductase (RCCR), yielding a fluorescent Chl-catabolite (FCC). RCCR of Arabidopsis thaliana was expressed in a functional form 13 and its crystal structure (with RCC bound) was elucidated.14 RCCR occurs in two stereo-divergent lines, which produce either the ‘primary’ Page 7 of 30 Chemical Society Reviews Phyllobilins-TutRev-BKräutler 2-May-14 7 FCC ( pFCC) or its C16-epimer, epi -pFCC (see Figure 4). It is a ferredoxin-dependent enzyme, homologous to the ‘ferredoxin-dependent bilin reductases’, which catalyze a range of reductive modifications of heme-derived bilins.15 RCCR is presumed to reduce RCC via single electron / proton transfer steps,14 for which electrochemical investigations with RCC provided a mechanistic model.16 pFCC was first identified from an enzyme extract from senescent leaves of oil seed rape, 17 epi -pFCC from a related system using leaves of sweet pepper. 6 So far, the critical absolute configuration at C16 of FCCs remains unassigned. pFCC and related FCCs are colourless tetrapyrroles that luminesce blue (at 450 nm) when excited with UV-light (at about 360 nm), making the detection of minute amounts of FCCs possible. 3 Figure 4. Chlorophyll a/b is degraded, in senescent chloroplasts, via pheophorbide a (Pheo a) and red Chl-catabolite (RCC) to the ‘primary’ fluorescent Chl-catabolite ( pFCC / epi -pFCC), following the ‘phyllobilin/PaO’ path.6 Chemical Society Reviews Page 8 of 30 Phyllobilins-TutRev-BKräutler 2-May-14 8 2.2.
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